Development of 5 Components Coupling Reaction of Dienes

本研究的目的是开发五组分偶联反应。也就是说，在烷基卤化物和三羰基亚硝基氰酸盐存在的情况下，讨论了1,3-丁烯或1,2-二烯的酰基金属化，并讨论了与乙醇醇解后所得到的铁配合物与1,2-二（二苯基膦）乙烷（DPPE）的羰基插入反应。结果表明，1,2-二烯或1,3-丁二烯5组分、2分子三羰基亚硝基氰酸盐一氧化碳、烷基卤化物和乙醇完成了立体选择性和区域选择性的偶联反应。在四丁基三羰基亚硝基氰酸铵（tafe）存在下，1,2-二烯（烯）与烷基卤化物反应生成（η^3-2-酰基1）二羰基亚硝基配合物，并伴有烯基金属化，产率高。在tafe存在下，1,3-丁二烯与烷基卤化物反应生成（η^3-1-酰基甲基化1）二羰基亚硝基配合物，并伴有1,3-丁二烯的酰基金属化反应，产率较高。得到的铁配合物与DPPE在烯丙基配体的阻碍较少的位置反应得到ε-acy1-β， γ-不饱和酰基铁配合物。随后，酰基配合物与乙醇醇解得到相应的ε-酰基1-β， γ-不饱和羧酸酯。以类似的方式，由1,2-二烯（烯）和烷基卤化物与tafe得到（η^3-2-酰基烯1）二羰基1-亚硝基龙配合物，得到β-酰基1-β， γ-不饱和酰基龙配合物，然后与乙醇醇解得到β-酰基1-β， γ-不饱和羧酸酯。

In this study, the aim is development of 5 components coupling reaction. That is, in the presence of alkyl halides and tricarbonylnitrosylferrate, acylmetallation of 1,3-butaienes or 1,2-dienes was discussed and the carbonyl insertion reaction of the resulting iron complexes with 1,2-bis(diphenylphosphino)ethane (DPPE) following the alcoholysis with ethanol was discussed. In the result, the coupling reaction of 5 components of 1,2-dienes or 1,3-butadienes, two molecules of carbon monoxide from tricarbonylnitrosylferrate, alkyl halides, and ethanol completes stereo- and regioselectively.In the presence of tetrabutylammmonium tricarbonylnitrosylferrate (TBAFe), 1,2-dienes (allenes) and alkyl halides reacted to give (η^3-2-acylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of allenes in good yields.In the presence of TBAFe, 1,3-butadienes and alky1 halides reacted to give (η^3-1-acylmethylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of 1,3-butadienes in good yields. The resulting iron complexes reacted with DPPE at the less hindered site of the allylic ligand to give ε-acy1-β, γ-unsaturated acyliron complexes. In succession, the alcoholysis of the acyliron complexes with ethanol gave the corresponding ε-acy1-β, γ-unsaturated carboxylic esters. In a similar manner, (η^3-2-acylally1) dicarbony1-nitrosyliron complexes obtained from 1,2-dienes (allenes) and alky1 halides with TBAFe gave the β-acy1-β, γ-unsaturated acyliron complexes followed by alcoholysis with ethanol to give the β-acy1-β, γ-unsaturated carboxylic esters.